CN108232163A - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN108232163A CN108232163A CN201810033854.8A CN201810033854A CN108232163A CN 108232163 A CN108232163 A CN 108232163A CN 201810033854 A CN201810033854 A CN 201810033854A CN 108232163 A CN108232163 A CN 108232163A
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- carbon
- sulphur
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of anode material for lithium-ion batteries and preparation method thereof, the porous carbon that is prepared by of its anode material for lithium-ion batteries forms carbon sulphur nanoparticle with sulphur, carbon sulphur nanoparticle is loaded to bilayer graphene film, form composite membrane (CSG), composite membrane covers one layer of " skin " formed by graphene film and porous carbon again, forms carbon sulphur nanoparticle graphene/porous carbon membranes (CSG/PC).Porous carbon membranes in the present invention are made of graphene film and porous carbon, its thickness is about 1 μm, positioned at the bottom of carbon sulphur nanoparticle graphene film, the shuttle effect of polysulfide can be effectively prevented, while the quick movement for electronics and lithium ion provides effective channel.
Description
Technical field
The present invention relates to lithium ion cell electrode technical field more particularly to a kind of anode material for lithium-ion batteries and its systems
Preparation Method.
Background technology
Lithium ion battery is up to as a kind of high power capacity energy storage system of novel great development prospect, theory than energy
2600Wh/Kg.Sulphur reacts to form Li completely with lithium metal2S, electrode reaction S8+16Li++16e-→8Li2S, the theoretical ratio of sulphur
Capacity is up to 1672mAh/g.In addition, elemental sulfur rich reserves, cheap and toxicity in nature is relatively low, and therefore, simple substance
Sulphur is one of current very attractive positive electrode.But active material sulphur and final discharging product Li in lithium-sulfur cell2S
It is the insulator of electronics and ion, and the intermediate product polysulfide in discharge process is soluble in electrolyte, causes lithium sulphur electric
Pond has that active material utilization is low, poor circulation in actual use.
Method solves the problems, such as these of lithium-sulfur cell there are two types of at present, and a kind of method is that elemental sulfur is loaded to porous carbon
In material, particularly in mesoporous material, polysulfide to be prevented to be dissolved in electrolyte.In addition, mesoporous material can also be carried effectively
The loading of high-sulfur.Another method is to be utilized respectively carbon nanotube, carbon fiber or conductive polymer to form interlayer, and will
It is placed between sulfur electrode and partition board to prevent the shuttle of polysulfide.Both the above method can improve lithium sulphur to a certain extent
The chemical property of battery, still, the dissolving of polysulfide and shuttle phenomenon can not be prevent completely by only relying on mesoporous material.Together
When, the screen effect that interlayer shuttles to polysulfide is also extremely limited.And blocked up interlayer can also influence electronics and ion
Movement.Therefore, inhibit the diffusion of polysulfide and improve the research emphasis that sulphur anode cycle electric conductivity is sulphur positive electrode.
Invention content
The present invention is small for sulfur electrode specific capacity existing for sulphur positive electrode of the prior art, and energy density is low, cycle
The problems such as poor performance, provides a kind of sulphur loading height, and active utilization rate is high, and energy density is high, the sulphur anode material of good cycle
Material.
The present invention provides a kind of easy to operate, at low cost, compound suitable for preparation graphene carbon material/sulphur of industrialized production
The method of positive electrode.
Lithium sulfur battery anode material of the present invention is a kind of carbon-sulphur nanoparticle-graphene/porous carbon membranes.It is utilized
Porous carbon forms carbon-sulphur nanoparticle with sulphur, and carbon-sulphur nanoparticle is loaded to bilayer graphene film, forms composite membrane (CSG), multiple
It closes film and covers one layer of " skin " formed by graphene film and porous carbon again, form carbon-sulphur nanoparticle-graphene/porous carbon membranes
(CSG/PC)。
In the carbon-sulphur nanoparticle-graphene/porous carbon membranes (CSG/PC), porous carbon membranes thickness is about 1 μm, positioned at carbon-
The bottom of sulphur nanoparticle-graphene film.
In the carbon-sulphur nanoparticle-graphene/porous carbon membranes (CSG/PC), the mass percent of elemental sulfur for 15%~
70%.
The preparation method of material involved in the present invention：
(1) by porous carbon and active sulfur with 1:3 mixing, mixture is placed in reaction kettle, is heated to 190 under an ar atmosphere
DEG C, 12 hours are kept the temperature, obtains carbon-sulphur nanoparticle.
(2) by carbon-sulphur nanoparticle and graphene oxide with 10:1 is uniformly mixed, and the solution of 1mg/mL is prepared into, by solution
Suction filtration forms carbon-sulphur/graphene oxide membrane.
(3) graphene oxide in porous carbon is uniformly mixed, forms mixed solution, mixed liquor is filtered to form graphite oxide
Alkene-carbon film.It adds in carbon-sulphur nanoparticle-graphene oxide mixed solution to continue to filter, obtains carbon-sulphur nanoparticle-graphite oxide
Alkene/porous carbon membranes.
(4) gained carbon-sulphur nanoparticle-graphene oxide/porous carbon membranes are placed in hydrazine steam, are restored under the conditions of 90 DEG C
48 hours, obtain carbon-sulphur nanoparticle-graphene/porous carbon membranes.
Carbon-sulphur nanoparticle is formed by the use of porous carbon as template and sulphur in the present invention, improves the loading of sulphur
(68.1%).
The conductivity of the invention for using graphene that can not only improve CSG/PC as the carrier of carbon-sulphur nanoparticle, but also
Graphene can effectively prevent the shuttle effect of polysulfide.
Porous carbon membranes in the present invention are made of graphene film and porous carbon, and thickness is about 1 μm, positioned at carbon-sulphur nanometer
The bottom of grain-graphene film can effectively prevent the shuttle effect of polysulfide, while be the quick movement of electronics and lithium ion
Effective channel is provided.
Carbon-sulphur nanoparticle-graphene/porous carbon membranes prepared by the present invention have excellent as lithium sulfur battery anode material
Chemical property, and capacity is up to 1163mAh/g, good cycling stability (1000 capacity retention ratios 82% of cycle), library
Human relations efficiency reaches 100%.
The present invention provides a kind of load of sulphur is high, active material utilization efficiency is high, and energy density is high, during for lithium-sulfur cell
The new lithium-sulfur battery composite cathode material that can be high of cycle.
Description of the drawings
Fig. 1 is that the SEM of carbon-sulphur nanoparticle-graphene/porous carbon membranes schemes；
Fig. 2 is that the SEM of carbon-sulphur nanoparticle-graphene layer schemes, and as can be seen from the figure carbon-sulphur nanoparticle uniformly disperses
In graphene layer；
Fig. 3 is graphene, the thermogravimetric curve of carbon-sulphur nanoparticle-graphene/porous carbon membranes and sulphur, as can be seen from the figure
Sulfur content reaches 68.1% in carbon-sulphur nanoparticle-graphene/porous carbon membranes；
Fig. 4 is the cyclic voltammetry curve that carbon-sulphur nanoparticle-graphene/porous carbon membranes positive electrode is applied to lithium-sulfur cell；
Fig. 5 is carbon-sulphur nanoparticle-three times charging and discharging curve of the graphene/porous carbon membranes positive electrode under the conditions of 0.1C；
Fig. 6 is 1000 cycle performance figures of the carbon-sulphur nanoparticle-graphene/porous carbon membranes positive electrode in 1C.
Specific implementation method
Embodiment 1：500mg porous charcoals ball with 1500mg active sulfurs is mixed, mixture is placed in 100mL reaction kettles,
190 DEG C are heated under Ar atmosphere again, 12 hours is kept the temperature, obtains carbon-sulphur nanoparticle.
100mg carbon-sulphur nanoparticle with 10mg graphene oxides is uniformly mixed, water is added to be prepared into the solution of 1mg/mL, it will
Solution filters to form carbon-sulphur/graphene oxide membrane.Graphene oxide in porous carbon is uniformly mixed, forms mixed solution, it will be mixed
Liquid is closed to filter to form graphene oxide-carbon film.It adds in carbon-sulphur nanoparticle-graphene oxide mixed solution to continue to filter, obtain
Carbon-sulphur nanoparticle-graphene oxide/porous carbon membranes.
Gained carbon-sulphur nanoparticle-graphene oxide/porous carbon membranes are placed in hydrazine steam, 48 are restored under the conditions of 90 DEG C
Hour, obtain carbon-sulphur nanoparticle-graphene/porous carbon membranes
Embodiment 2：300mg porous charcoals ball with 900mg active sulfurs is mixed, mixture is placed in 100mL reaction kettles, then
190 DEG C are heated under Ar atmosphere, 12 hours is kept the temperature, obtains carbon-sulphur nanoparticle.
80mg carbon-sulphur nanoparticle with 8mg graphene oxides is uniformly mixed, water is added to be prepared into the solution of 1mg/mL, it will be molten
Liquid filters to form carbon-sulphur/graphene oxide membrane.Graphene oxide in porous carbon is uniformly mixed, mixed solution is formed, will mix
Liquid filters to form graphene oxide-carbon film.Add in carbon-sulphur nanoparticle-graphene oxide mixed solution continue to filter, obtain carbon-
Sulphur nanoparticle-graphene oxide/porous carbon membranes.
Gained carbon-sulphur nanoparticle-graphene oxide/porous carbon membranes are placed in hydrazine steam, 48 are restored under the conditions of 90 DEG C
Hour, obtain carbon-sulphur nanoparticle-graphene/porous carbon membranes
Battery assembles and test：Carbon-sulphur nanoparticle-graphene oxide/porous carbon membranes are struck out to the electricity of a diameter of 12mm
Pole piece is as anode, and using metal lithium sheet as cathode, electrolyte is 1M LiTFSI/DOL:DME(1:1), in argon gas glove box
In be assembled into CR2032 button cells.At room temperature using sweep speed as 0.1mV/s under conditions of carry out cyclic voltammetry (figure
4).Charge-discharge test (Fig. 5) is carried out with the current density of 0.1C at room temperature, test result is shown, specific capacity 1268mAh/
g.Long circulating test (Fig. 6) is carried out with the current density of 1C, test result shows carbon-sulphur nanoparticle-graphene oxide/porous carbon
Film (CSG/PC) recycles 1000 capacity retention ratios 82% as anode, lithium-sulfur cell, and coulombic efficiency reaches 100%, with
Simple carbon-sulphur nanoparticle-graphene oxide membrane (CSG) is high as the cyclical stability of anode.
Claims (6)
1. a kind of anode material for lithium-ion batteries, which is characterized in that the positive electrode is a kind of carbon-sulphur nanoparticle-graphite
Alkene/porous carbon membranes forms carbon-sulphur nanoparticle using porous carbon and sulphur, carbon-sulphur nanoparticle is loaded to bilayer graphene film,
Composite membrane (CSG) is formed, composite membrane covers one layer of " skin " formed by graphene film and porous carbon again, forms carbon-sulphur nanometer
Grain-graphene/porous carbon membranes (CSG/PC).
A kind of 2. anode material for lithium-ion batteries according to claim 4, which is characterized in that the carbon-sulphur nanoparticle-graphite
In alkene/porous carbon membranes (CSG/PC), porous carbon membranes thickness is about 1 μm, positioned at the bottom of carbon-sulphur nanoparticle-graphene film.
A kind of 3. anode material for lithium-ion batteries according to claim 4, which is characterized in that the carbon-sulphur nanoparticle-graphite
In alkene/porous carbon membranes (CSG/PC), the mass percent of elemental sulfur is 15%~70%.
4. a kind of preparation method of anode material for lithium-ion batteries, which is characterized in that include the following steps：
(1) porous carbon with active sulfur is mixed, mixture is placed in reaction kettle, be heated to 190 DEG C under an ar atmosphere, heat preservation 12
Hour, obtain carbon-sulphur nanoparticle；
(2) carbon-sulphur nanoparticle with graphene oxide is uniformly mixed, is prepared into the solution of 1mg/mL, solution is filtered to be formed carbon-
Sulphur/graphene oxide membrane；
(3) graphene oxide is uniformly mixed in porous carbon, formed mixed solution, mixed liquor is filtered to be formed graphene oxide-
Carbon film adds in carbon-sulphur nanoparticle-graphene oxide mixed solution and continues to filter, obtains carbon-sulphur nanoparticle-graphene oxide/more
Hole carbon film；
(4) gained carbon-sulphur nanoparticle-graphene oxide/porous carbon membranes are placed in hydrazine steam, it is small that 48 is restored under the conditions of 90 DEG C
When, obtain carbon-sulphur nanoparticle-graphene/porous carbon membranes.
A kind of 5. preparation method of anode material for lithium-ion batteries according to claim 4, which is characterized in that carbon-sulphur nanometer
Grain is with graphene oxide with 10:1 mass ratio is uniformly mixed.
6. a kind of preparation method of anode material for lithium-ion batteries according to claim 4, which is characterized in that porous carbon and work
Property sulphur is with 1:3 mass ratioes mix.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972467A (en) * | 2013-02-06 | 2014-08-06 | 中国科学院金属研究所 | Lithium-sulfur battery multilayer composite positive electrode and preparation method thereof |
| CN105826523A (en) * | 2016-03-17 | 2016-08-03 | 北京理工大学 | Lithium-sulfur battery positive pole material and preparation method thereof |
-
2018
- 2018-01-15 CN CN201810033854.8A patent/CN108232163A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972467A (en) * | 2013-02-06 | 2014-08-06 | 中国科学院金属研究所 | Lithium-sulfur battery multilayer composite positive electrode and preparation method thereof |
| CN103972467B (en) * | 2013-02-06 | 2016-01-13 | 中国科学院金属研究所 | A kind of lithium-sulfur cell MULTILAYER COMPOSITE positive pole and preparation method thereof |
| CN105826523A (en) * | 2016-03-17 | 2016-08-03 | 北京理工大学 | Lithium-sulfur battery positive pole material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| MINGKAI LIU等: "A highly conductive carbon–sulfur film with interconnected mesopores as an advanced cathode for lithium–sulfur batteries", 《CHEMICAL COMMUNICATIONS》 * |
| 张超: "石墨烯复合材料的制备、结构及性能研究", 《中国博士学位论文全文数据库·工程科技I辑》 * |
| 杨希: "基于石墨烯的超级电容器和锂-硫电池制备与性能研究", 《中国博士学位论文全文数据库·工程科技I辑》 * |
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Application publication date: 20180629 |